MM0800090

Jour. Myan. Acad. Arts & Sc. 2005 Vol. III. No. 1 Chemistry

Synthesis of a - Ahimina (Corundum) and its Application

Nay Thwe Kyi , Kyaw Myo Naing , Tin Tin Aye J and Nyunt Wynn

Abstract
This paper described the preparation of aluminium isopropoxide from
aluminium sheet at different heating times. Aluminium sheet is found to
have a reaction with absolute isopropyl alcohol and mercury (II) chloride as
a qatalyst under nitrogen atmosphere. Aluminium isopropoxide was
characterized by NMR, XRD and IR. Aluminium isopropoxide serves as a.
molecular precursor to derive pure alumina gel by hydrolysis under both
homogeneous and heterogeneous conditions. Pyrolysis to this alumina gel
transforms it into a -alumina (corundum) at 1200°C. The phase
transformation during pyrolysis was characterized by XRD, SEM and TEM.
The a - alumina (corundum) has porous crystalline nature with high
surface area, which may be used as efficient adsorbent packing material in
column chromatography for the seperation of vitamin A from the leaves,
a -alumina can be also used in catalysis.
Keywords: aluminium isopropoxide, alumina gel, a-alumina
(corundum), pyrolysis phase transformation, catalysis.

Introduction
In liquid phase chromatography, silica gel (SiO2, H2O), cellulose, or
alumina (A12O3) is used as a solid adsorbent. (Moore & Dalrymple 1976),
especially alumina (solid adsorbent) is used in the separation of leaf pigments
and vitamin A in magarine. The alumina column prevents caking and
initiates separation of carotene and other interfering substances.
Aluminas are obtained from the variety of sources. Among them,
the hydrolysis of aluminium aikoxide into alumina which has the porous
crystalline form and high surface area.
Aluminium aikoxide is one of the metal alkoxides which was
developed after world war II. Today the alkoxides of alkali metals,
magnesium, titaniumm zirconium, antimony and aluminium alkoxides are
commercially important.(Kark & Othmer 1982).

1- Lecturer, Department of Chemistry, University of Sittway.

2. Associate Professor, Department of Chemistry. University of Yangon.
. Ass °ciate Professor, Department of Chemistry, University of Yangon.
• Emeritus ..Professor, Department of Chemistry, University of Yangon.
 DISCLAIMER

Portions of this document may be

illegible in electronic image products.
Images are produced from the best
available original document
 50 Jour. Myan. Acad. Arts & Sc. 2005 Vol. III. No. 1 Chemistry

Particularly the aluminium alkoxides of C3 arid C-4 alcohols,

such as aluminium isopropoxide and aluminium sec-butoxide are of
technical importance. In aluminium alkoxide, superficially there appear to
be three (OR) groups around the central Al5 but in fact the alkoxides
are polymeric, eg, aluminium isopropoxide is trimeric, but slowly
rearranges to the tetramer on standing (Davison. 1961).
Aluminium alkoxides are easily soluble in aromatic and
chlorinated hydrocarbons, but springly soluble in alcohols. It is sensitive
to moisture11 and therefore dry storage is essential.
Aluminium alkoxides are used extensively as molecular
precursors such as mesoporous oxides from thermal treatment of
aluminium alkoxides (Yang. 1998), alumina gel from hydrolysis of
aluminium alkoxides (Stump£,etf ah 1950) and the alumina and silica
sols from aluminium isopropoxide with tetraethylorthosilicate (Gulnihal.
2002).
The present paper involves the studies on aluminium
isopropoxide from aluminium sheet and purified by isopropyl alcohol,
alumina gel from the sol-gel hydrolysis of aluminium isopropoxide,
activated alumina from pyrolysis of alumina gel at different heating
times. This activated alumina gel can be used in chromatography,
dehydrating agents, ion exchange materials and catalysts.
Alumina occurs in a variety of forms. It is common constituent
of many rocks and minerals but it is also found in the free state as the
oxide or hydroxide. Aluminium oxide occurs in nature as corundum
which has the crystalline type. Aluminium hydroxide may be prepared
in amoiphous Jor crystalline forms. Freshly precipitated aluminium
hydroxide is amorphous but aging gives crystals (Searle. 1959).
The hydrolysis of aluminium isopropoxide gives alumina xerogel
(porous). Amorphous alumina xerogel was prepared in an aqueous
medium and amorphous alumina aerogel was prepared in a non-aqueous
medium. Foster and Keys showed that the best areogels and xerogels
have about the same activity (Kerker. 1977).
Several crystalline hydrates exist namely the a and p -trihydrate
(gibbsite and bayerite) and the a and p monohydrate (boehmite and
diaspore) and anhydrous alumina namely a -alumina (corundum) (Day &
Hill 1953).

fgytf^
Jour. Myan. Acad. Arts & Sc. 2005 Vol. III. No. 1 Chemistry 51

Thermal decomposition or the various alumina hydrates yield a

number of crystalline variations of alumina which are transition stages in
a process eventually yielding anhydrous alumina corundum. Alumina the
amorphous crystallines to the a - crystalline modification at a temperature
between 500-1000°C and at higher temperatures it is converted to the a -form,
known as corundum (Searle & Grimshaw. 1959).
Corundum is stable above 450±5°c. Diaspore is stable 280 to
450±5°C and boehmite apparently is stable between I55°C and 280°C.
Gibbsite is unstable above 155°C. Bayerite is unstable above 155°C,
while the indications are that it is less stable than gibbsite below this
temperature (Laubengayer & Weisz. 1943).
During drying, some of the crystalline phases such as the a - and
(3 trihydrate and a -monohydrate have been examined by X-ray
diffraction analysis. The dried alumina gel can be activated by heating
and is porous with high surface area, which makes it useful as an
adsorbent (Harris., et al. 1958).

Experimental
The chemical suppliers were from British Drug House (BDH)
Chemical Co., Ltd., England Kanto Chemical Co., Ltd., Japan and Fisons
Scientific Equipment, Laughbrough, England. These chemicals were used
as it was received unless otherwise stated.
The apparatus used included a balance (E. Mettler, Switzerland),
a magnetic heating and stirring (Volts - 230, Hz ~ 50, UK by Bibby
Sterilini Ltd.), X-ray diffraction (XRD Ragaku D-Max 2200, Japan), a
muffle furnace (Model L - 3333, Australia), a vacuum oven (Gallenkamp)
Edward EB 3A vacuum pump and compressor, England and a glass
ware (Pyrexglass).
The experimental work was carried out in two categories. The
first involve the preparation of aluminium isopropoxide by the reaction
of aluminium sheet, purified isopropyl alcohol and mercury II chloride
used as catalyst under nitrogen atmosphere. The solution mixture was
placed in a round-bottomed flask, provided with an efficient reflux
condenser. The flask is gently warmed in a stream-bath and gentle
refluxing maintained at different heating times. The product was purified
52 Jour. Myan. Acad. Arts & Sc 2005 Vol. m . No. 1 Chemistry

by distillation under vacuum. This fine product was characterized by

melting point, NMR, XRD and JR.
The second included the preparation of the alumina gel by hydrdlysing
aluminium isopropoxid under homogeneous and heterogeneou conditions.
Under homogeneous condition, the solution of aluminium isopropoxide in
absolute isopropyl alcohol with an equal volume of a solution of water
in isopropyl alcohol were stirred for about 3 hrs. The gel was formed by
centrifuging and was washed once with isopropyl alcohol. The sample
was dried by vaccum oven.
Under heterogeneous condition, the solution of aluminium
isopropoxide in benzene with an equal volume of water were stirred for
about 15 mins. The gel was formed and then it was mixed with
isopropyl alcohol. After the separation of the mixture, the gel was washed
with water three times and washed once with isopropyl alcohol.
Then the alumina gels from two methods were heated in a
furnace at selected temperatures(ambient temperature, 200°C, 400°C,
800°C and 1200°C) to obtain activated alumina. For each temperature
the alumina gel was kept for 1-hr. The phase transformation of this
alumina gel was then characterized by XRD, SEM and TEM.

Results and Discussion

In the synthesis of aluminium isopropoxide, excess amount of
purified isopropyl alcohol and aluminium . such as aluminium sheet,
aluminium powder with mercury II chloride as catalyst were used at
different heating times. Amoung them, the synthesis using aluminium
sheet is efficient. The yield % of aluminium isopropoxide prepared
from aluminium sheet at different heating times were shown in Table 1.
Table 1. Effect of reaction time on the aluminium isopropoxide
prepared using aluminium sheet (95± 5°C)
No Time Yield (%)
1 1 -
2 3 15.00
3 5 87.00
4 7 88.13
5 9 88.25

mMmmSm^imSmfiwmm
Jour. Myan. Acad. Arts & Sc. 2005 Vol. III. No. 1 Chemistry 53

The heating times were different about ± 2 hrs from one another.
Increasing the heating time, the yield % also increases. But when the
heating time is above 5 hrs the yield % becomes close to one another.
On the basis of these results. 7 hrs of heating time is suitable for the
optimum time.
Aluminium isopropoxide was characterized by NMR spectroscopy.
Aluminium isopropoxide in CDC13 was recorded at 300 MHz NMR
spectrophotometer and the spectrum is shown in Figure 1. It consists of
.three doublets and two septets. The hight field doublet representing 36
equivalent protons reveals 12 terminal methyl groups which absorb at 8 1.13
ppm (with J = 6 Hz).
The two doublets, absorb at lower field are two sets of non-
equivalent methyl protons oi bridge isopropyl groups, each set containing
6 methyl groups appear at 6 1.29 ppm and 1.48 ppm (withJ = 6Hz).
Two septets at 8 4.53 ppm and 4.23 ppm represent two non-
equivalent methine protons of isopropoxy groups. On the basis of the
NMR spectrum, this compound can be tetrameric aluminium
isopropoxide. The chemical shift value and interpreation of aluminium
isopropoxide is reported in Table - 2.

x,..

Figure 1. HNMR spectrum of aluminium isopropoxide

54 Jour. Myan. Acad. Arts & Sc. 2005 Vol. III. No. 1 Chemistry

Figure 2. XRD spectrum of aluminium isopropoxide

Figure 3 (a). XRD spectrum of alumina gel at ambient temperature

 J

Jour. Myan. Acad. Arts & Sc. 2005 Vol. HI. No. 1 Chemistry 55

XtO I jrtt, tt^.,

Figure 3 (b). XRD spectrum of alumina gel at 200°C

709

Figure 3 (c ) . XRD spectrum of alumina gel at 400°C

56 Jour. Myan. Acad. Arts & Sc. 2005 Vol. III. No. 1 Chemistry

Figure 3 ( d ) . XRD spectrum of alumina gel at 800°C

Li „ , 1 il il

xtointxx.
Figure 3 (e ) . XRD spectrum of alumina gel at 1200°C (homogeneous
condition
 Acad. Arts & Sc 2005 Vol. ffl. No. 1 Chemistry 57

**•

jiii<«W*'.^
mmm¥^^^^^immmmm

:
• ?-••"<••-: :'-
A
:"'-f'" ••!:•.•«:;:•:•••.:
i I

Figure 3 ( f ) . XRD spectrum of alumina gel at 1200°C (heterogeneous condition)

Table 2 . NMR spectrum assignment for aluminium isopropoxide

5(ppm) Multiplicity Integration Assignment

1.48 doublet (J- 6 Hz) 6 11 •CH^ "

1.29 doublet (J~ 6 Hz) 6H -CH

CH3 '

1.13 doublet (J= 6 Hz) 6H

~ 3 X CH 3

4.53 septet (J= 6 Hz) 1H

"~JVCH3
/CH,
4.28 septet (J= 6 Hz) 1H
\
58 Jour. MysH. Acsd. Arts & Sc 2005 Vol. III. No. 1 Chemistry

X-ray diffractogram also indicates the crystalline nature of

aluminium isopropoxide as shown in figure 2.
The alumina gel was prepared by hydrolysing aluminium
isopropoxide under homogeneous and heterogeneous conditions at
ambient temperature. The X-ray diffractogram of this alumina gel from
two methods are similar pattern in- Figure 3 (a) which indicates the
amorphous nature. This alumina gel was pyrolysed at selected
temperature (200°, 400°, 800° and 1200°C). During pyrolysis, the weight
loss% of alumina gel is shown in Table-3
Table 3 . Tm weight loss % of alumina gel at certain various
temperature.
Mass (g) . Mass (g)
Temperature . Weight . %Bifference
No (before (after
Loss(%) theorectical
pyrolysis) pyrclysis)

1 200 0.5 0.4295 14.1 4,19

-
2 400 -0.5 0.3781 24.38 4.66
3 800 0,5 03297 34.06 4.38
4 1200 0,5 0.2787 44.26 4.91
Increasing the pyrolysis temperature, the weight loss % were
increased. This means that at lower temperature, the water molecule
was left in the alumina gel. At 1200°C, all the water molecules were
released from the alumina gel, which indicates the crystalline nature.
X-ray diffractograrns can also be used to identify these results.
After pyrolysis at selected temperatures such as 200°C, 400°C and 800°
C, the XRD patterns of alumina gels from two methods are similar
patterns in Figure 3-b, 3-c and 3-d. At these temperatures, the XRD
patterns exhibit broad maxima, characteristic of amorphous material.
At 1200°C the different XRD patterns of alumina gels from two
methods are shown in Figure 3-e and 3-f. Figure 3-e is shown the
crystallization of aluminium oxide (but not corundum) which was
obtained from homogeneous condition.
The nature of a - alumina (corundum) which takes place is
evidenced by sharp peak as shown in Figure 3.f. XRD data for
synthetic a - alumina and standard alumina are shown in Table 4.

^
Jour, Myan. Acad. Arts & Sc, 2005 Vol. Ill, No. 1 ChcKiistrv 59

Table 4 : X-Ray diffeaction data for synthetic a - alumia and

standard alumina.
a-, Alumina (Standard) a- A3iiniina (Synche tic)

I(%) * •d(A) 2-Thsta I(</o) <i(A) 2-Theta

i.

100 2.0834 43394 100 • 2 0823 43.420

92.0 2.5488 35,181 92,.0 5461 35.220
r
80.1 1.6001 57.555 8CLl 1 ,5999 57.560

In this paper, the preparation of aluminium isopropoxide from

aluminium sheet was made? and NMR, XRD analysis were carried out,
And then a - alumina was prepared by pyrolysing the alumina gel ,from
the hydrolysis of aluminium isopropoxide u nder homogenrneous and
heterogeneous' unditions.
The phase transformation of alumina gel was assessed during
pyrolysing. • Alumia is used as a solid adsorbent in chromatography to
separate chlorophyll, and p - carotene from the leaf pigmems.

Brown, L.M., et al. 1969. Anal Chem., 41, pp. 1243-50

Davison, B.K. 1961. Chem <& Ind., pp. 39-40.
Day, M.K.B, Hill, V.J. 1953. /. Phy. Chem., 57, 946.
Harris, M.R., et al. 1958. J ofAppl Chem., S, pp. 586-89.
Kark, R.E. and Othmer, D.F. 1982. Encyclopedia of Chemical Technology., I, pp 1-17,
Kerker, M., et al. 1977. "Colloid and Interface Science". Academic Press, Inc., New York, 1,
95.
Laubengayer, A.W. and Weisz, R.S. 1943. JAm. Chem. Soc, 6S, 247.
Oliver, J.G., et al. 1969. J. Inorg. Nucl Chem., 31, pp. 1906 - 1613.
Searle, A.B. and Grimshaw, R.W. 1959. " The Cheitiistry and Physics of Clays and other
Ceramic Materials", London. 3rd Ed, 318,
Smith, W.E. and Anderson, A.R. 1960. U.S. Pat, Dec. 20.